Tutorial: Rheology of Soft Materials

Sujit S. Datta
Department of Physics
Harvard University
What Is Rheology?
The quantitative study of the manner in which materials deform and flow.

● Describe the mechanical constitutive relationship for a material (response to force):

Prescribe/measure

(Elastic solid)

(Viscous liquid)

● What kinds of materials do we study in our lab?

Soft materials - generally isotropic, disordered, both elastic and viscous components.
○ Allen, Lolo, Stefan: Biopolymer networks
○ Jim, Shmuel: Biofilms, polymers
○ Joris: Colloidal suspensions/gels, microgels, polymers
○ Sujit and Dustin: Colloidal suspensions, emulsions
Outline Of This Tutorial
● Basic definitions: stress/strain, affine/non-affine, flows, viscoelasticity, shear modulus

● Some different responses: Maxwell, Kelvin-Voigt, SGR

● How to actually measure things: controlled/stress strain, viscometry, geometries

● Two examples:
○ Soft glassy emulsions
○ Colloidal gels

● Other types of measurements/topics of interest:

○ SRFS
○ Non-linear (shear thinning/shear thickening)
○ Shear-banding
○ Yield stress
○ Pre-stress
○ LAOS
Basic Definitions: Stress/Strain

Plate of area Pull with force

Strain:
Stress:

● Note: here, only consider shear flows/stresses; no extensional flows or normal stresses
Basic Definitions: Affine/Non-Affine
Affine
○ Uniform deformation
○ Local strain = macroscopic strain
Non-Affine
Major subject of current research!
Significant influence on rheology of:
○ Biopolymers (Lolo))
○ Microgels (Joris)
○ Emulsions (Simulations)
○ Shear-banding of suspensions
Basic Definitions: Viscoelasticity
● See video

● Materials have different mechanical responses depending on timescale of measurement

(Elastic solid) (Viscous liquid)

● How to quantify this? Stress relaxation modulus Gr(t).

○ There are many equivalent ways to measure this! Different preferences based on
experimental method, tradition, etc.
Stress
Step strain

Measure Relaxation time

t=0 Time
Basic Definitions: Complex Shear Modulus
● Another approach: frequency-domain

Strain Stress

Time

Storage of Viscous
elastic energy dissipation

1/Relaxation time
G’

G’’

Frequency
One Model: Maxwell (Low Frequency Relaxation)
● Elastic solid in series with viscous dashpot
(e.g. entangled polymer solution)

● Timescale:

● Can derive functional form of G’, G’’ as a function of frequency

~1/Relaxation time
G’

G’’

Frequency
● This model captures stress relaxation behavior better
One Model: Kelvin-Voigt (Low Frequency Elasticity)
● Elastic solid in parallel with viscous dashpot

● Timescale:

● G’, G’’ as a function of frequency are very simple

G’

~1/Relaxation time

G’’

Frequency
● This model captures creep recovery behavior better
Phenomenological Model: Sollich’s Soft Glassy Rheology
● Energy barriers >> thermal energy; these are due to microscopic structure of material

3 Energy ○ Each mesoscopic region has own yield

2
energy; distribution of yield energies
4
1
○ Hopping activated by noise temperature
x; this is related to how jammed
Local Strain l

○ Hopping time-scale is given by

1 2 3 4 phenomenological attempt frequency
How To Actually Measure Things

TA AR-G2 (2 of them) Anton-Paar MCR 501 TA ARES G2

○ Stress-controlled
○ Most versatile set of
geometries
○ Standard solvent trap
...talk to Lolo.
○ Stress-controlled (claim
also strain-controlled)
○ Array of geometries
○ High-performance
solvent trap
...talk to Joris.
○ True strain-control
○ Array of geometries
○ Standard solvent trap
(high-performance
maybe coming soon)
...talk to Sujit/Jim.
Strain versus Stress Controlled
Strain Controlled
○ Good for oscillatory measurements
○ Good for fixed shear rate measurements
○ Motors are really good - good for weak
materials
○ Very sensitive torque transducers
○ Easier to damage
Stress Controlled
○ OK for oscillatory measurements
○ Good for fixed stress measurements
○ Good for creep measurements
○ Drag cup motors often cannot do low
stresses well
○ EC motors often have more inertial effects
○ Often assumes certain type of material
response
How To Actually Measure Things

Single/Double-Gap Couette Parallel Plates Cone-Plate

○ Large volumes (~9 mL) ○ Small volumes (~0.1-3 mL) ○ Small volumes (~0.1’s mL)
○ Very sensitive ○ Inhomogeneous strain field ○ Homogeneous strain field
○ Homogeneous strain field
How To Actually Measure Things
● Different types of measurement:
○ Frequency sweep (characteristic timescales, solid-like plateaus, gel scaling, ...)
○ Strain sweep (yielding behavior, linear regime, ...)
○ Flow curves (yield stress, viscosity, shear-banding, ...)
○ Stress-relaxation (characteristic timescales)
○ SRFS (relaxation spectrum)
 Example: Colloidal Suspensions
Long-time fluidization Elastic response Response of suspending fluid
of material
Modulus

Densely-packed emulsions*

1
G’

G’’

Colloidal Gels

*Note: G’’ of dense emulsions has a frequency0.5 response at Frequency

high frequencies, not discussed here
One Example: Densely-Packed Emulsions (Mason)
One Example: Densely-Packed Emulsions (Mason)
One Example: Densely-Packed Emulsions (Mason)
One Example: Densely-Packed Emulsions (Mason)
Another Example: Colloidal Gels (Trappe)
Another Example: Colloidal Gels (Trappe)
Another Example: Colloidal Gels (Trappe)
Strain Rate Frequency Superposition
● Structural relaxation of a material happens at a characteristic timescale ; this is
typically way longer than experimental timescales

● Shearing at high enough strain rate can make a material structurally relax; this is like
speeding up the structural relaxation to a new timescale

● Phenomenological expression:

● Instead of holding strain constant or frequency constant, hold strain rate constant
Strain Rate Frequency Superposition
Strain Rate Frequency Superposition
Strain Rate Frequency Superposition
Strain Rate Frequency Superposition
Other Stuff Of Current Interest
● Shear-thickening: role of hydrodynamics, etc.

● Shear-banding: why do some suspensions shear-band?

● Yield stress: do soft materials have a “true” yield stress, or does this just depend on
measurement time?

● Pre-stress measurements: for biopolymer networks that stress stiffen, oscillating about
large stress value gives valuable information

● LAOS: shapes of waveforms at large amplitudes can yield interesting information

Questions?